JP7592651B2 - Matrix resin reinforced with hybrid polyamide particles - Google Patents

Description

The present invention relates generally to pre-impregnated composite materials (prepregs) used to make high performance composite parts, particularly suitable for use as aerospace components. The present invention relates to epoxy resins reinforced with thermoplastic materials and used as the resin matrix of such prepregs. More particularly, the present invention relates to prepregs that include polyamide particles as one of the thermoplastic materials used to reinforce the resin matrix.

Composite materials are typically composed of two main components: a resin matrix and reinforcing fibers. Composite materials are often required to perform in demanding environments, such as aerospace, where the physical limits and properties of the composite parts are critical.

Pre-impregnated composite materials (prepregs) are widely used in the manufacture of composite parts. Pre-pregs are a combination that typically includes uncured resin and fiber reinforcement in a form ready for molding and curing into a final composite part. By pre-impregnating the fiber reinforcement with resin, manufacturers can carefully control the amount and location of resin that is impregnated into the fiber network, ensuring that the resin is distributed in the network as needed. It is well known that the relative amounts of fiber and resin in a composite part, as well as the distribution of resin within the fiber network, affect the structural properties of the part.

Prepregs are the preferred material for use in the manufacture of load-bearing or primary structural components, particularly aerospace primary structural components such as wings, fuselages, bulkheads and control surfaces. It is important that these components have sufficient strength, damage tolerance, and other requirements routinely established for such components and structures.

Fiber reinforcements commonly used in aerospace prepregs are multidirectional woven fabrics or unidirectional tapes containing fibers running parallel to one another. The fibers are typically in the form of bundles of many individual fibers or filaments called "tows." The fibers or tows can also be chopped and randomly oriented in the resin to form nonwoven mats. These various fiber reinforcement structures are combined with carefully controlled amounts of uncured resin. The resulting prepregs are typically placed between protective layers and rolled up for storage or transport to the manufacturing facility. The combination of carbon fiber with an epoxy resin matrix has become a common combination in aerospace prepregs.

Prepregs may be in the form of short segments of chopped unidirectional tape that are randomly oriented to form a nonwoven mat of chopped unidirectional tape. This type of prepreg is called a "quasi-isotropic chopped" prepreg. Quasi-isotropic chopped prepregs are similar to more traditional nonwoven fiber mat prepregs, except that rather than chopped fibers, short lengths of chopped unidirectional tape (chips) are randomly oriented within the mat. This material is commonly used as a sheet molding compound to form parts and molds for use in manufacturing the parts.

The compressive and tensile strength of a cured composite part is largely determined by the individual properties of the reinforcing fibers and matrix resin, as well as the interaction between these two components. In addition, the fiber-to-resin volume ratio is an important factor. In many aerospace applications, it is desirable for composite parts to exhibit high compressive and tensile strength. The open-hole compression (OHC) test is the standard measure of compressive strength of composite materials. The open-hole tensile (OHT) test is also the standard measure of tensile strength of composite materials.

In many aerospace applications, it is desirable for composite parts to exhibit high compressive and/or tensile strength under both room temperature/dry and elevated temperature/humid conditions. However, maintaining high compressive and tensile strength often adversely affects other desirable properties such as damage tolerance and interlaminar fracture toughness.

Selecting a resin with a higher modulus can be an effective way to improve the compressive strength of a composite. However, this can tend to reduce damage tolerance, typically measured by a decrease in compressive properties such as compression after impact (CAI) strength. Thus, it can be difficult to simultaneously increase both compressive strength and/or tensile strength without adversely affecting damage tolerance.

Multiple layers of prepreg are commonly used to form composite parts with laminated structures. Delamination in such composite parts is an important failure mode. Delamination occurs when two layers peel away from each other. Important design limit factors include both the energy required to initiate a delamination and the energy required to propagate it. Delamination initiation and growth are often determined by examining Mode I and Mode II fracture toughness. Fracture toughness is typically measured using composites with unidirectional fiber orientation. Interlaminar fracture toughness of composites is quantified using G1c (Double Cantilever Beam) and G2c (End Notch Flex) tests. In Mode I, the pre-crack laminate failure is dominated by delamination forces, and in Mode II, the crack propagates due to shear forces.

One approach to improve the interlaminar fracture toughness of parts made from carbon fiber/epoxy resin prepregs has been to introduce thermoplastic sheets as interleaves between the layers of the prepreg. However, this approach tends to result in a stiff, non-sticky material that is difficult to use. Another approach has been to add thermoplastic particles to the epoxy resin so that a resin interlayer containing the thermoplastic particles is formed between the fiber layers of the final part. Polyamides have been used as such thermoplastic particles. It is also known to include thermoplastic toughening agents in epoxy resins. Toughening agents such as polyethersulfone (PES) or polyetherimide (PEI) are dissolved in the epoxy resin before application to the carbon fiber. Thermoplastic toughened epoxy resins containing a combination of both thermoplastic toughening particles and thermoplastic toughening agents have been used in combination with carbon fiber to make aerospace prepregs.

The epoxy resin matrix may include one or more types of epoxy resin. It is known that various combinations of different types of epoxy resins can result in significant changes in the properties of the final composite part. The curing agent used to cure the epoxy resin matrix can also substantially affect the properties of the final composite part. When formulating epoxy resins for use as the resin matrix of an aerospace prepreg, it is difficult to predict whether a new combination of epoxy resin type and curing agent will give the desired combination of properties required for the aerospace part. This is especially true when thermoplastic toughening agents and thermoplastic particles form part of the epoxy resin formulation. Thus, much testing is required when formulating a new thermoplastic toughened epoxy resin to determine whether the resin is suitable for use as a resin matrix for an aerospace prepreg.

While existing aerospace prepregs are suitable for their intended use of providing strong, damage tolerant composite parts, there remains a continuing need to provide aerospace prepregs that can be used to make composite parts that exhibit a desirable combination of high tensile and compressive strength (OHC and OHT) while maintaining high levels of damage tolerance (CAI) and interlaminar fracture toughness (G1c and G2c).

The present invention provides a pre-impregnated composite material (prepreg) that can be molded to form composite parts that have high levels of strength and also have high levels of damage tolerance and interlaminar fracture toughness.

The pre-impregnated composite material of the present invention is composed of reinforcing fibers and an uncured resin matrix. The uncured resin matrix includes a resin component consisting of one or more epoxy resins, a thermoplastic toughening agent, and a hardener. The uncured resin matrix further includes a thermoplastic particle component including polyamide particles. In a preferred embodiment, the polyamide particles are hybrid polyamide particles composed of a mixture of semi-crystalline and crystalline polyamides, respectively.

The invention also includes methods for making the prepregs and methods for forming the prepregs into a wide variety of composite parts. The invention also includes composite parts made using the improved prepregs.

It has been found that resins having matrix resin formulations such as those described above can be used to form moldable prepregs to form composite parts having unexpectedly high levels of interlaminar fracture toughness.

The above and many other features and attendant advantages of the present invention will be better understood by reference to the following detailed description taken in conjunction with the accompanying drawings.

FIG. 1 is a perspective view of an aircraft illustrating an exemplary primary aircraft structure that may be fabricated using composite materials according to the present invention.

1 is a partial view of a helicopter rotor blade illustrating an exemplary primary aircraft structure that may be fabricated using composite materials according to the present invention.

The uncured epoxy resin composition according to the present invention may be used in a wide variety of situations where a thermoplastic toughened epoxy resin matrix is desired. The uncured epoxy resin composition may be used alone, but is typically used as a matrix resin in combination with a fibrous support to form a composite comprised of a fibrous support and a resin matrix. The composite may be in the form of a prepreg, a partially cured prepreg, or a fully cured final part. The term "uncured" as used herein in reference to a prepreg; a resin prior to impregnation of a fibrous support; a resin matrix formed upon impregnation of a fibrous support with a resin; or a composite, refers to an item that may be somewhat cured, but is not fully cured to form a final composite part or structure.

Although uncured composite materials may be used for any intended purpose, they are preferably used in manufacturing parts for aerospace airframes, such as commercial and military aircraft. For example, uncured composite materials may be used to create non-primary (secondary) aircraft structures. However, uncured composite materials are preferably used in structural applications, such as primary aircraft structures. Primary aircraft structures or parts are elements of either fixed-wing or rotorcraft aircraft that are subject to significant stresses during flight and are essential for the aircraft to maintain controlled flight. Uncured composite materials may also be used in other structural applications, generally to create load-bearing parts and structures.

1 shows a fixed-wing aircraft at 10 including several exemplary primary aircraft structures and parts that may be fabricated using uncured composite materials according to the present invention. Exemplary primary parts or structures include a wing 12, a fuselage 14, and a tail assembly 16. The wing 12 includes several exemplary primary aircraft parts such as an aileron 18, a leading edge 20, a wing slat 22, a spoiler 24, a trailing edge 26, and a trailing edge flap 28. The tail assembly 16 also includes several exemplary primary parts such as a rudder 30, a fin 32, a horizontal stabilizer 34, an elevator 36, and a tail 38. FIG. 2 shows the outer end of a helicopter rotor blade 40 including a wing spar 42 and an outer surface 44 as a primary aircraft structure. Other exemplary primary aircraft structures include the wing spars, as well as various flanges, clips, and connectors that connect the primary parts together to form the primary structure.

The pre-impregnated composite material (prepreg) of the present invention can be used to replace existing prepregs used to form composite parts in the aerospace industry and any other application requiring high structural strength and damage tolerance. The present invention involves replacing the existing resins used to make the prepreg with the resin formulation of the present invention. Thus, the resin formulation of the present invention is suitable for use as a matrix resin in conventional prepreg manufacturing and curing processes.

The pre-impregnated composite material of the present invention is comprised of reinforcing fibers and an uncured resin matrix. The reinforcing fibers can be any of the conventional fiber configurations used in the prepreg and composite sheet molding industries. Carbon fibers are preferred as reinforcing fibers.

Preferred resins used to form the resin matrix (matrix resin) include a resin component consisting of a hydrocarbon epoxy novolac resin in combination with a trifunctional epoxy resin and optionally a tetrafunctional epoxy resin. The matrix resin further includes a hybrid thermoplastic particle component, a thermoplastic toughening agent, and a hardener.

The hydrocarbon epoxy novolac resin preferably has a dicyclopentadiene backbone and is commercially available from Huntsman Corporation (The Woodlands, Texas) as TACTIX 556. This type of hydrocarbon novolac resin is referred to herein as dicyclopentadiene novolac epoxy resin. The chemical formula for TACTIX 556 is:

TACTIX 556 is an amber to dark semi-solid hydrocarbon epoxy novolac resin with an epoxy index (ISO 3001) of 4.25-4.65 eq/kg and an epoxy equivalent weight (ISO 3001) of 215-235 g/eq. The viscosity (ISO 9371B) of TACTIX 556 at 79°C is 2250 mPa·s. Dicyclopentadiene epoxy novolac resins other than TACTIX 556 may be used in place of TACTIX 556 as long as the resins have the same chemical formula and properties. For example, another suitable dicyclopentadiene epoxy novolac resin is XD-1000-2L, available from Nippon Kayaku Co., Ltd. (Chiyoda-ku, Tokyo). TACTIX 556 is the preferred hydrocarbon epoxy novolac resin for use in accordance with the present invention.

When a tetrafunctional epoxy resin is included in the preferred resin component, the amount of hydrocarbon epoxy novolac resin present in the uncured resin can vary from 8 to 20 weight percent based on the total weight of the uncured resin matrix. Preferably, the uncured resin contains 10 to 17 weight percent dicyclopentadiene hydrocarbon epoxy novolac resin. Uncured resin formulations containing 13 to 15 weight percent dicyclopentadiene hydrocarbon epoxy novolac resin are especially preferred. In this embodiment of the invention, referred to herein as DEN/TRIF/TETF matrix resin, the uncured resin component consists of a dicyclopentadiene epoxy novolac resin, a trifunctional epoxy resin, and a tetrafunctional epoxy resin.

In the DEN/TRIF/TETF matrix resin, a preferred exemplary trifunctional epoxy resin is triglycidyl para-aminophenol. Triglycidyl para-aminophenol is commercially available from Huntsman Advanced Materials (The Woodlands, Texas) under the trade name Araldite MY0510. Another suitable trifunctional epoxy resin is triglycidyl meta-aminophenol. Triglycidyl meta-aminophenol is commercially available from Huntsman Advanced Materials (The Woodlands, Texas) under the trade name Araldite MY0600 and from Sumitomo Chemical Co., Ltd. (Osaka, Japan) under the trade name ELM-120. Other trifunctional epoxy resins may be used, provided they have the same or similar properties as those of triglycidyl para-aminophenol or triglycidyl meta-aminophenol.

In the DEN/TRIF/TETF matrix resin embodiment, an exemplary tetrafunctional epoxy resin is N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM), commercially available as Araldite MY720 and MY721 from Huntsman Advanced Materials (The Woodlands, Texas) or as ELM 434 from Sumitomo Chemical Co., Ltd. (Chuo-ku, Tokyo). Other tetrafunctional epoxy resins may be used, provided they have the same or similar properties as those of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

In DEN/TRIF/TETF matrix resins, the total amount of trifunctional and tetrafunctional epoxy resins can vary from 35 to 45 weight percent based on the total weight of the uncured resin. The weight ratio of trifunctional to tetrafunctional resins is preferably 1.0:1.5 to 1.5:1.0. The weight ratio of trifunctional to tetrafunctional resins is especially preferably 1.1:1.0 to 1.3:1.0.

In another preferred embodiment of the present invention, the resin component contains only dicyclopentadiene novolac epoxy resin and triglycidyl aminophenol epoxy resin. In the resin component of this embodiment, referred to herein as DEN/TRIF matrix resin, the dicyclopentadiene novolac epoxy resin is present in a range of 4% to 30% by weight based on the total weight of the uncured resin matrix. Preferably, the dicyclopentadiene novolac epoxy resin is present in a range of 17% to 27% by weight based on the total weight of the uncured resin matrix. More preferably, the dicyclopentadiene novolac epoxy resin is present in a range of 20% to 24% by weight based on the total weight of the uncured resin matrix.

In DEN/TRIF matrix resins, the triglycidyl aminophenol epoxy resin is present in the range of 20% to 55% by weight based on the total weight of the uncured resin matrix. Preferably, the triglycidyl aminophenol epoxy resin is present in the range of 26% to 36% by weight based on the total weight of the uncured resin matrix. More preferably, the triglycidyl aminophenol epoxy resin is present in the range of 29% to 33% by weight based on the total weight of the uncured resin matrix. Triglycidyl meta-aminophenol is a preferred type of triglycidyl aminophenol epoxy resin for DEN/TRIF matrix resins.

In the DEN/TRIF matrix resin, the weight ratio of triglycidyl aminophenol epoxy resin to dicyclopentadiene novolac epoxy resin can vary from 1:1 to 10.5:1. The preferred weight ratio range of triglycidyl aminophenol epoxy resin to dicyclopentadiene novolac epoxy resin is 1.2:1 to 2.5:1. Most preferred is a weight ratio of triglycidyl aminophenol epoxy resin to dicyclopentadiene novolac epoxy resin of about 2.0:1.

The uncured resin matrix according to the present invention also includes a thermoplastic particle component containing one or more thermoplastic particles. Exemplary thermoplastic particles are polyamide particles formed from the polymeric condensation product of bis(4-aminocyclohexyl)methane, including its methyl derivatives, and an aliphatic dicarboxylic acid selected from the group consisting of decanedicarboxylic acid and dodecanedicarboxylic acid. Bis(4-aminocyclohexyl)methane and its methyl derivatives are referred to herein as the "amine component." Bis(4-aminocyclohexyl)methane is also known as 4,4'-diaminocyclohexylmethane. Polyamide particles of this type and methods for their manufacture are described in U.S. Pat. Nos. 3,936,426 and 5,696,202, the contents of which are incorporated herein by reference.

The formula for the amine component of the polymeric condensation product is:

where _R2 is hydrogen and _R1 is either methyl or hydrogen.

In formula AC-G, when R ₁ is methyl and R ₂ is hydrogen, the formula of the resulting monomer unit of the polymeric condensation product can be represented as follows:

The molecular number of the polymer condensation product ranges from 14,000 to 20,000, with a molecular number of about 17,000 being preferred.

The polyamide particles should have a particle size of less than 100 microns. The particle size is preferably in the range of 5 to 60 microns, more preferably 10 to 30 microns. The average particle size is preferably 15 to 25 microns. The shape of the polyamide particles may be regular or irregular. For example, the particles may be substantially spherical or may be jagged shaped particles.

One exemplary polyamide particle is made from a polyamide having the above formula (AC-G) where the amine component of the polymeric condensation product has both R ₁ 's and both R ₂ 's are hydrogen. Such polyamide particles can be made from a polymeric condensation product of 3,3'-dimethyl-bis(4-aminocyclohexyl)-methane and 1,10-decanedicarboxylic acid. The polyamide particles are made by combining 13,800 grams of 1,10-decanedicarboxylic acid and 12,870 grams of 3,3'-dimethyl-bis(4-aminocyclohexyl)methane with 30 grams of 50% aqueous phosphoric acid, 150 grams of benzoic acid, and 101 grams of water in a heated containment vessel. The mixture is stirred in a pressure autoclave until homogeneous. After compression, depressurization, and degassing steps, the polyamide condensation product is extruded as strands, passed through cold water, and granulated to form polyamide particles. Polyamide particles where R ₁ are both methyl and R ₂ are both hydrogen can also be made from GRILAMID TR90, commercially available from EMS-Chime (Sumter, South Carolina), which is a polymeric condensation product of 3,3′-dimethyl-bis(4-aminocyclohexyl)-methane and 1,10-decanedicarboxylic acid.

Another exemplary polyamide particle is made from a polyamide having the above formula (AC-G) where R ₁ and R ₂ are both hydrogen, the amine component of the polymeric condensation product. Such polyamide particles may be made in a manner similar to that described above, except that the polyamide is a polymeric condensation product of bis(4-aminocyclohexyl) -methane and 1,10-decanedicarboxylic acid. The formula for the amine component of this preferred polymeric condensation product is as follows:

Formula AC-I corresponds to the above general formula (AC-G) in which R ₁ and R ₂ are hydrogen. Furthermore, the hydrogen groups present at the 2-, 5-, and 6-positions of the cyclohexane group implied in general formula (AC-G) are specifically shown in formula AC-I.

When the amine component is bis(4-aminocyclohexyl)methane (formula AC-I), the formula of the monomer unit of the polymeric condensation product of AC-I and 1,10-decanedicarboxylic acid is the same as formula I above, except that each cyclohexyl group or methyl group attached to the 3- or meta-position on the ring is replaced with hydrogen as shown in formula II.

The molecular number of the polymeric condensation product formed from monomer unit II ranges from 14,000 to 20,000, with a molecular number of about 17,000 being preferred. The polyamide particles formed from this polymeric condensation product should also have a particle size of less than 100 microns. It is also preferred that the particle size ranges from 3 to 60 microns, more preferably from 10 to 30 microns. It is also preferred that the average particle size is from 15 to 25 microns. The shape of the polyamide particles can also be regular or irregular. For example, the particles can be substantially spherical or can be jagged shaped particles.

The monomer units corresponding to formula II may be in the form of stereoisomers in which the nitrogen groups attached to the cyclohexyl ring are in the cis-cis, cis-trans or trans-trans orientation. Polyamides formed from monomer II may contain one, two or all three stereoisomers. Polyamides containing a mixture of all three monomer stereoisomers tend to be amorphous, while polyamides composed primarily of one stereoisomer tend to be semi-crystalline. Processing conditions are controlled to give the desired mixture of stereoisomers. Trogamid CX9704 is an exemplary amorphous polyamide that is a mixture of all three isomeric forms of formula II. Trogamid CX9704 is available from Evonik, Mobile, Alabama. Trogamid CX9705 is an exemplary semi-crystalline polyamide composed primarily of the trans-trans isomeric form of formula II. Trogamid (registered trademark in some countries) CX9705 is available from Evonik (Mobile, Alabama).

Preferred polyamide particles are hybrid polyamide particles, each hybrid polyamide particle containing a mixture of the amorphous and semi-crystalline polyamides described above. The hybrid polyamide particles are made by dissolving the desired amounts of amorphous and semi-crystalline polyamides in a suitable solvent, such as ethylene glycol, to form a hybrid mixture. The hybrid mixture is then extruded and/or processed according to conventional polyamide processing procedures to remove the solvent and form the desired hybrid particles, each containing a mixture of amorphous and semi-crystalline polyamides.

The hybrid polyamide particles should have a particle size of less than 100 microns. The hybrid polyamide particle size is preferably in the range of 3 to 60 microns, more preferably 10 to 30 microns. The average hybrid polyamide particle size is preferably 15 to 25 microns. The shape of the hybrid polyamide particles may also be regular or irregular. For example, the hybrid polyamide particles may be substantially spherical or may be jagged shaped particles.

The hybrid polyamide particles are made from a hybrid mixture containing amounts of amorphous polyamide and semi-crystalline polyamide such that the resulting hybrid polyamide particles each contain 20-80 wt.% amorphous polyamide and 20-80 wt.% semi-crystalline polyamide, based on the total weight of the hybrid polyamide particles. Preferably, each hybrid polyamide particle contains 65-75 wt.% amorphous polyamide and 25-35 wt.% semi-crystalline polyamide, based on the total weight of the hybrid polyamide particles. Most preferred are hybrid polyamide particles containing 70±1 wt.% amorphous polyamide and 30±1 wt.% semi-crystalline polyamide, based on the total weight of the hybrid polyamide particles.

As used herein, hybrid polyamide particles are identified by the relative amounts of amorphous and semi-crystalline polyamide present in each hybrid polyamide particle. For example, a hybrid polyamide particle containing a mixture of 70% by weight CX9704 polyamide (amorphous) and 30% by weight CX9705 polyamide (semi-crystalline) would be identified as hybrid polyamide particle 70A/30SC, and a hybrid polyamide particle containing a mixture of 30% by weight CX9704 polyamide (amorphous) and 70% by weight CX9705 (semi-crystalline) polyamide would be identified as hybrid polyamide particle 30A/70SC.

Differential scanning calorimetry (DSC) is a standard test used to measure the crystalline and amorphous nature of polymers. Table A shows the DSC test results of an exemplary amorphous polyamide (TROGAMID CX9704), an exemplary semi-crystalline polyamide (TROGAMID CX9705), and an exemplary hybrid polyamide composed of a mixture of TROGAMID CX9704 and TROGAMID CX9705, which were used to make hybrid polyamide particles 70A/30SC and 30A/70SC.

The above description of the polyamide component, including polyamide particles that are hybrid polyamide particles, is not limited to polyamides having monomer units of formula II. Any polyamide that is used to toughen epoxy resins and can be made in amorphous and semi-crystalline forms can be used to form hybrid polyamide particles.

The thermoplastic particle component may also include one or more other types of polyamide particles typically used in thermoplastic toughened epoxy resins, including, for example, polyamide (PA) 11, PA6, PA12, PA6/PA12 copolymer, PA4, PA8, PA6.6, PA4.6, PA10.10, PA6.10, and PA10.12.

An exemplary thermoplastic particle component contains a first group of polyamide particles that does not contain crosslinked polyamide and a second group of polyamide particles that contains crosslinked polyamide.

The first group of polyamide particles can be either hybrid polyamide particles as described above, or polyamide particles that do not contain crosslinked polyamide and are typically used in thermoplastic toughened epoxy based prepregs. Such particles can be composed of polyamide (PA) 11, PA6, PA12, PA6/PA12 copolymer, PA4, PA8, PA6.6, PA4.6, PA10.10, PA6.10 and PA10.12. Non-crosslinked polyamide particles are commercially available from several sources. Suitable non-crosslinked polyamide 12 particles are available from Kobo Products under the trade name SP10L. SP10L particles contain greater than 98% by weight of PA12. The particle size distribution is from 7 microns to 13 microns, with an average particle size of 10 microns. The density of the particles is 1 g/ ^cm3 . The PA12 particles are preferably at least 95% by weight of PA12, excluding moisture content. It is also preferred that the hybrid polyamide particles are at least 95% by weight, excluding moisture content, of amorphous and semi-crystalline polyamide.

Other suitable non-crosslinked particles are available from Arkema (Colombes, France) under the trade names Orgasol 1002 powder and Orgasol 3803 powder. Orgasol 1002 powder is composed of 100% PA6 particles with an average particle size of 20 microns. Orgasol 3803 is composed of particles that are a copolymer of 80% PA12 and 20% PA6, with an average particle size of 17-24 microns. Orgasol 2002 is a powder composed of non-crosslinked PA12 particles that may also be used in the first particle group.

Preferred non-crosslinked polyamide particles for the first group of thermoplastic particles are polyamide 11 particles, which are also commercially available from several sources. Polyamide 11 particles are available from Arkema (Colombes, France) under the trade name Rislan PA11. These particles contain more than 98% by weight PA11 and have a particle size distribution between 15 microns and 25 microns. The average particle size is 20 microns. The density of the Rislan PA11 particles is 1 g/ ^cm3 . It is preferred that the PA11 particles are at least 95% by weight PA11, excluding the moisture content.

A second group of thermoplastic polyamide particles are those that contain crosslinked polyamide on the surface of the particle, in the interior of the particle, or both. Crosslinked polyamide particles can be made from polyamide that is crosslinked prior to particle formation, or non-crosslinked polyamide particles can be treated with a suitable crosslinking agent to produce crosslinked polyamide particles.

Suitable crosslinked particles contain crosslinked PA11, PA6, PA12, PA6/PA12 copolymer, PA4, PA8, PA6.6, PA4.6, PA10.10, PA6.10 and PA10.12. Any of the crosslinkers commonly used to crosslink polyamides are suitable. Examples of crosslinkers are epoxy crosslinkers, isocyanate crosslinkers, carbodiimide crosslinkers, acyllactam crosslinkers and oxazoline crosslinkers. Preferred crosslinked particles are PA12 particles containing PA12 crosslinked with an epoxy crosslinker. Procedures used to crosslink thermoplastic polymers, including polyamides, are known. See, for example, U.S. Pat. No. 6,399,714, U.S. Pat. No. 8,846,818 and U.S. Patent Application Publication No. 2016/0152782 A1. The contents of these three references are incorporated herein by reference.

Crosslinked PA12 particles are commercially available from Arkema (Colombes, France) under the trade name ORGASOL 2009 polyamide powder, also known as CG352. The PA12 particles present in the ORGASOL 2009 polyamide powder are composed of at least 40% PA12 crosslinked with an epoxy-based crosslinker. The ORGASOL 2009 crosslinked polyamide particles have an average particle size of 14.2 microns, with only 0.2% of the particles having a diameter greater than 30 microns. The melting point of the ORGASOL 2009 crosslinked particles is 180°C. The specific surface area of the ORGASOL 2009 particles is 1.9, and the moisture content of the particles is 0.34%.

The crosslinked polyamide particles should each contain 40-70% crosslinked polyamide. Preferably, the crosslinked polyamide particles should each contain 40-60% crosslinked polyamide.

Preferably, both the non-crosslinked and crosslinked polyamide particles should have a particle size of less than 100 microns. The particle size is preferably in the range of 5 to 60 microns, more preferably 5 to 30 microns. The average particle size is preferably 5 to 20 microns. The shape of the particles may be regular or irregular. For example, the particles may be substantially spherical or may be jagged shaped particles. The average particle size of the non-crosslinked particles is preferably larger than the average particle size of the crosslinked particles. Preferably, the average particle size of the non-crosslinked particles is in the range of 15 to 25 microns and the average particle size of the crosslinked particles is in the range of 10 to 20 microns.

The thermoplastic particle component is present in the range of 5% to 20% by weight based on the total weight of the uncured resin matrix. Preferably, 7 to 17% by weight of the thermoplastic particle component is present. When a combination of crosslinked and non-crosslinked particles is used, the relative amounts of non-crosslinked and crosslinked particles can vary. The weight ratio of non-crosslinked to crosslinked particles can range from 4:1 to 1.5:1. Preferably, the weight ratio of non-crosslinked to crosslinked particles ranges from 3.5:1 to 2.5:1. A combination of hybrid polyamide particles and crosslinked particles is a preferred thermoplastic particle component for use in embodiments of the DEN/TRIF matrix resin.

Hybrid polyamide particles are preferred particles for use in the thermoplastic component. Hybrid polyamide particles may be used in combination with a wide variety of epoxy resin components other than the DEN/TRIF and DEN/TRIF/TETF epoxy resin components. For example, hybrid polyamide particles may be used to toughen epoxy resins that include a difunctional epoxy resin as all or part of the epoxy resin component. Difunctional epoxy resins include any suitable epoxy resins having two epoxy functional groups. Difunctional epoxy resins may be saturated, unsaturated, cycloaliphatic, cycloaliphatic, or heterocyclic. Difunctional epoxies may be used alone or in combination with multifunctional epoxy resins to form the resin component. Resin components containing only multifunctional epoxies are also possible.

By way of example, difunctional epoxy resins include those based on (optionally brominated) bisphenol F, diglycidyl ethers of bisphenol A, glycidyl ethers of phenol-aldehyde adducts, glycidyl ethers of aliphatic diols, diglycidyl ethers, diethylene glycol diglycidyl ethers, Epikote, Epon, aromatic epoxy resins, epoxidized olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imidines and amides, glycidyl ethers, fluorinated epoxy resins, or any combination thereof. The difunctional epoxy resin is preferably selected from diglycidyl ethers of bisphenol F, diglycidyl ethers of bisphenol A, diglycidyl dihydroxynaphthalene, or any combination thereof. Most preferred is the diglycidyl ether of bisphenol F. Diglycidyl ethers of bisphenol F are commercially available from Huntsman Advanced Materials (Salt Lake City, Utah) under the trade names Araldite GY 281 and GY 285, and from Ciba-Geigy (Tarrytown, New York) under the trade name LY 9703.

The hybrid polyamide particles may be used to toughen epoxy resin components including trifunctional and/or tetrafunctional epoxy resins other than those mentioned above. The multifunctional epoxy resins may be saturated, unsaturated, cycloaliphatic, cycloaliphatic, or heterocyclic. Suitable multifunctional epoxy resins include, by way of example only, those based on phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldehyde adducts; glycidyl ethers of dialiphatic diols; diglycidyl ethers; diethylene glycol diglycidyl ether; aromatic epoxy resins; dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers; epoxidized olefins; brominated resins; aromatic glycidyl amines; heterocyclic glycidyl imidines and amides; glycidyl ethers; fluorinated epoxy resins or any combination thereof.

Trifunctional epoxy resins have three epoxy groups substituted directly or indirectly in the para or meta orientation on phenyl rings in the backbone of the compound. Tetrafunctional epoxy resins have four epoxy groups substituted directly or indirectly in the meta or para orientation on phenyl rings in the backbone of the compound.

The phenyl ring may be further substituted with other suitable non-epoxy substituents. Suitable substituents include, by way of example only, hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxyl, aryl, aryloxyl, aralkyloxyl, aralkyl, halo, nitro, or cyano. Suitable non-epoxy substituents may be attached to the phenyl ring at the para or ortho positions, or at a meta position not occupied by an epoxy group. Suitable tetrafunctional epoxy resins include N,N,N',N'-tetraglycidyl-m-xylylenediamine (available under the name Tetrad-X from Mitsubishi Gas Chemical Company, Inc., Chiyoda-ku, Tokyo, Japan) and Erisys GA-240 (available from CVC Chemicals, Morristown, NJ).

Suitable trifunctional epoxy resins include, by way of example only, those based on phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldehyde adducts; aromatic epoxy resins; dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers; epoxidized olefins; brominated resins; aromatic glycidyl amines and glycidyl ethers; heterocyclic glycidyl imidines and amides; glycidyl ethers; fluorinated epoxy resins or any combination thereof.

In embodiments of the DEN/TRIF matrix resin, the total amount of polyamide particles in the uncured resin can vary from 9 to 21 weight percent based on the total weight of the uncured resin. Preferably, the total amount of polyamide particles in the uncured resin ranges from 11 to 19 weight percent based on the total weight of the uncured resin matrix. More preferably, the total amount of polyamide particles in the uncured resin ranges from 12 to 17 weight percent based on the total weight of the uncured resin matrix.

In a preferred embodiment, the thermoplastic particle component comprises a combination of polyimide particles and hybrid polyamide particles. This particle combination is the preferred thermoplastic particle component for use in the DEN/TRIF/TETF matrix resin embodiment.

A preferred polyimide particle is commercially available as P84 polyimide molding powder from HP Polymer GmbH, Lenzig, Austria. Suitable polyamide particles are also commercially available from Evonik Industries, Austria, under the trade designation P 84 NT. The polyimide used to make the particles is disclosed in U.S. Pat. No. 3,708,458, the contents of which are incorporated herein by reference. The polyimide is made by combining benzophenone-3,3',4,4'-tetracarboxylic dianhydride with a mixture of 4,4'-methylenebis(phenylisocyanate) and toluene diisocyanate (2,4- or 2,6-isomers). Amine analogs may be used in place of the aromatic isocyanates and diisocyanates. The CAS registration number for the polyimide is 58698-66-1.

Polyimide particles are comprised of the repeating monomer formula:

wherein 10-90% of the R groups in the entire polymer are of the formula:

and the remaining R groups in the polymer are

It is.

The polyimide particles in the powder typically range in size from 2 microns to 35 microns. A preferred polyimide powder contains particles ranging in size from 2 to 30 microns with an average particle size ranging from 5 microns to 15 microns. Preferably, at least 90% by weight of the polyimide particles in the powder are in the size range of 2 microns to 20 microns. The shape of the polyimide particles can be regular or irregular. For example, the particles can be substantially spherical or can be jagged shaped particles.

The polyimide particles contain at least 95 weight percent polyimide. Small amounts (up to 5 weight percent) of other materials may be included in the particles as long as they do not adversely affect the overall properties of the particles.

The glass transition temperature (Tg) of the polyimide particles should be approximately 330°C and the density of the individual particles is 1.34 grams/cubic centimeter. The linear thermal expansion coefficient of the particles is 50.

The total amount of thermoplastic particles in the uncured DEN/TRIF/TETF matrix resin embodiment is preferably 10-20 weight percent based on the total weight of the uncured resin. To obtain high delamination resistance, the weight ratio of hybrid polyamide particles to polyimide particles can range from 3.5:1.0 to 1.0:1.0. Preferably, the weight ratio between hybrid polyamide particles and polyimide particles is between 3.2:1.0 to 2.8:1.0. In a particularly preferred DEN/TRIF/TETF matrix resin, the amount of hybrid polyamide particles is 8-10 weight percent of the total weight of the uncured resin, and the amount of polyimide particles is 2-4 weight percent of the total weight of the uncured resin.

The uncured resin matrix includes at least one hardener. Suitable hardeners are those that promote the curing of the epoxy-functional compounds of the present invention, and in particular promote the ring-opening polymerization of such epoxy compounds. In particularly preferred embodiments, such hardeners include compounds that polymerize with the epoxy-functional compounds in their ring-opening polymerization. Two or more such hardeners may be used in combination.

Suitable hardeners include anhydrides, particularly polycarboxylic anhydrides, such as nadic anhydride (NA), methyl nadic anhydride (MNA - available from Aldrich), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (HHPA - available from Anhydrides and Chemicals Inc., Newark, NJ), methyl tetrahydrophthalic anhydride (MTHPA - available from Anhydrides and Chemicals Inc.), methyl hexahydrophthalic anhydride (MHHPA - available from Anhydrides and Chemicals Inc.), endomethylene tetrahydrophthalic anhydride, hexachloro endomethylene-tetrahydrophthalic anhydride (chlorentic anhydride - available from Velsicol Chemicals, Inc.), tetrahydrophthalic anhydride (tetrahydrophthal ... Corporation (Rosemont, Ill.), trimellitic anhydride, pyromellitic dianhydride, maleic anhydride (available from MA-Aldrich), succinic anhydride (SA), nonenylsuccinic anhydride, dodecenylsuccinic anhydride (available from DDSA-Anhydrides and Chemicals Inc.), polysebacic polyanhydride, and polyazelaic polyanhydride.

Further suitable curing agents are aromatic amines, such as 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, and polyaminosulfones, such as 4,4'-diaminodiphenylsulfone (4,4'-DDS, available from Huntsman), 4-aminophenylsulfone, and 3,3'-diaminodiphenylsulfone (3,3'-DDS). Also suitable curing agents include polyols, such as ethylene glycol (available from EG-Aldrich), poly(propylene glycol), and poly(vinyl alcohol); and phenol-formaldehyde resins, such as HRJ2210, HRJ-2255, and SP-1068, available from Schenectady Chemicals Inc., respectively. phenol-formaldehyde resins having an average molecular weight of about 550 to 650, p-t-butylphenol-formaldehyde resins having an average molecular weight of about 600 to 700, and p-n-octylphenol-formaldehyde resins having an average molecular weight of about 1200 to 1400, available from Ajinomoto USA Inc. (Schenectady, NY). Additionally, for phenol-formaldehyde resins, a combination of CTU guanamine and a phenol-formaldehyde resin having a molecular weight of 398, available as CG-125 from Ajinomoto USA Inc. (Teaneck, NJ), is also suitable.

Various commercially available compositions may be used as the curing agent in the present invention. One such composition is AH-154, a dicyandiamide type formulation available from Ajinomoto USA Inc. Suitable others include Ancamide 400, a mixture of polyamide, diethyltriamine, and triethylenetetraamine; Ancamide 506, a mixture of amidoamine, imidazoline, and tetraethylenepentamine; and Ancamide 1284, a mixture of 4,4'-methylenedianiline and 1,3-benzenediamine, available from Pacific Anchor Chemical, Performance Chemical Division, Air Products and Chemicals, Inc., Allentown, Pennsylvania. It is available from:

Additional suitable curing agents include imidazole (1,3-diaza-2,4-cyclopentadiene) available from Sigma Aldrich (St. Louis, MO), 2-ethyl-4-methylimidazole available from Sigma Aldrich, and boron trifluoride amine complexes such as Anchor 1170 available from Air Products & Chemicals, Inc.

Yet another suitable curing agent includes 3,9-bis(3-aminopropyl-2,4,8,10-tetroxaspiro[5.5]undecane, available from Ajinomoto USA Inc., as well as aliphatic dihydrazides also available from Ajinomoto USA Inc. as Ajicure UDH, and mercapto-terminated polysulfides available from Morton International, Inc., Chicago, Ill., as LP540.

The hardener is selected to provide cure of the matrix at a suitable temperature. The amount of hardener required to provide adequate cure of the matrix will vary depending on many factors, including the type of resin being cured, the desired cure temperature and cure time. Hardeners may also typically include cyanoguanidines, aromatic and aliphatic amines, acid anhydrides, Lewis acids, substituted ureas, imidazoles and hydrazines. The specific amount of hardener required for each particular situation can be determined by well-established routine experimentation.

Exemplary preferred curing agents include 4,4'-diaminodiphenyl sulfone (4,4'-DDS) and 3,3'-diaminodiphenyl sulfone (3,3'-DDS), both of which are commercially available from Huntsman Corporation (The Woodlands, Texas).

The hardener is present in an amount ranging from 10% to 30% by weight of the uncured resin matrix. In DEN/TRIF matrix resins, the hardener is present in an amount ranging from 17% to 27% by weight. More preferably, the hardener is present in an amount ranging from 21% to 25% by weight of the uncured resin matrix. In DEN/TRIF matrix resins, 4,4'-DDS is the preferred hardener. It is preferred that 4,4'-DDS is used as the only hardener in an amount ranging from 20% to 26% by weight. Small amounts (less than 5% by weight) of other hardeners, such as 3,3'-DDS, may be included if desired.

In DEN/TRIF/TETF matrix resins, the hardener is present in an amount ranging from 15% to 30% by weight of the uncured resin. Preferably, the hardener is present in an amount ranging from 20% to 30% by weight. 3,3'-DDS is the preferred hardener. 3,3'-DDS is preferably used as the sole hardener in an amount ranging from 24 to 28% by weight based on the total weight of the uncured resin. Small amounts (less than 5% by weight) of other hardeners, such as 4,4'-DDS, may be included if desired.

Accelerators may also be included to enhance or speed up the cure. Suitable accelerators are any uron compounds commonly used in the curing of epoxy resins. Specific examples of accelerators that may be used alone or in combination include N,N-dimethyl,N'-3,4-dichlorophenylurea (diuron), N'-3-chlorophenylurea (monuron), and preferably N,N-(4-methyl-m-phenylenebis[N',N'-dimethylurea] (e.g., Dyhard UR 500 available from Degussa).

The uncured resin matrix of the present invention also includes a thermoplastic toughening agent. Any suitable thermoplastic polymer may be used as the toughening agent. Typically, the thermoplastic polymer is added to the resin mix as particles that dissolve in the resin mixture upon heating, prior to the addition of the curing agent. Once the thermoplastic agent is substantially dissolved in the hot matrix resin precursor (i.e., the blend of epoxy resins), the precursor is cooled and the remaining ingredients (curing agent and insoluble thermoplastic particles) are added and mixed with the cooled resin blend.

Exemplary thermoplastic toughening agents/particles include any of the following thermoplastics, alone or in combination: polysulfones, polyethersulfones, polyetherimides, high performance hydrocarbon polymers, elastomers, and segmented elastomers.

A suitable toughening agent is, by way of example, particulate polyethersulfone (PES) sold under the tradename Sumikaexcel 5003P and available from Sumitomo Chemicals (New York, NY). Alternatives to 5003P are non-hydroxyl terminated grades such as Solvay polyethersulfone 105RP, or Solvay 1054P, available from Solvay Chemicals (Houston, TX). Densified PES particles may be used as the toughening agent. The form of the PES is not particularly important since the PES dissolves during the formation of the resin. Densified PES particles may be made according to the teachings of U.S. Pat. No. 4,945,154, the contents of which are incorporated herein by reference. Densified PES particles are also available commercially from Hexcel Corporation (Dublin, CA) under the tradename HRI-1. The average particle size of the reinforcing agent should be less than 100 microns to promote and ensure complete dissolution of the PES in the matrix.

In DEN/TRIF matrix resins, the toughening agent is present in the range of 5% to 15% by weight based on the total weight of the uncured resin matrix. Preferably, the toughening agent is present in the range of 7% to 12% by weight. More preferably, the toughening agent is present in the range of 8% to 11% by weight.

In DEN/TRIF/TETF matrix resins, the PES toughening agent is present in the range of 5% to 26% by weight based on the total weight of the uncured resin. Preferably, the toughening agent is present in the range of 7% to 14% by weight. The preferred amount of PES for use in making a resin with a relatively low minimum viscosity (25-45 poise) is 7-9% by weight based on the total weight of the uncured resin. The preferred amount of PES for use in making a resin with a relatively high minimum viscosity (55-75 poise) is 10-13% by weight based on the total weight of the uncured resin.

The matrix resin may also contain additional components such as performance enhancers or modifiers, so long as they do not adversely affect the adhesion and life of the prepreg or the strength and damage tolerance of the cured composite part. The performance enhancers or modifiers may be selected from, for example, core-shell rubbers, flame retardants, wetting agents, pigments/dyes, UV absorbers, anti-fungal compounds, fillers, conductive particles, and viscosity modifiers.

Exemplary core-shell rubber (CSR) particles are composed of a crosslinked rubber core, typically a copolymer of butadiene, and a shell composed of styrene, methyl methacrylate, glycidyl methacrylate, and/or acrylonitrile. The core-shell particles are usually provided as particles dispersed in an epoxy resin. The particle size range is typically 50-150 nm. Suitable CSR particles are described in detail in U.S. Patent Application Publication No. 2007/0027233 A1, the contents of which are incorporated herein by reference. A preferred core-shell particle is the MX core-shell particle available from Kane Ace (Pasadena, Texas). A preferred core-shell particle for inclusion in DEN/TRIF matrix resin is Kane Ace MX-418. MX-418 is supplied as a 25% by weight suspension of core-shell particles in a tetrafunctional epoxy resin. The core-shell particles in MX-418 are polybutadiene (PBd) core-shell particles with an average particle size of 100 nanometers.

Suitable fillers include, by way of example only, any of the following: silica, alumina, titania, glass, calcium carbonate, and calcium oxide, either alone or in combination.

Suitable conductive particles include, by way of example only, any of the following: silver, gold, copper, aluminum, nickel, conductive grade carbon, buckminsterfullerene, carbon nanotubes, and carbon nanofibers, either alone or in combination. Metal-coated fillers, such as nickel-coated carbon particles and silver-coated copper particles, may also be used.

Potato-shaped graphite (PSG) particles are a suitable conductive particle. The use of PSG particles in carbon fiber/epoxy resin composites is described in detail in U.S. Patent Application Publication No. 2015/0179298 A1, the contents of which are incorporated herein by reference. PSG particles are commercially available from NGS Naturgraphit (Germany) as SG25/99.95SC particles, or from Japan Power Graphite Co., Ltd. (Japan) as GHDR-15-4 particles. These commercially available PSG particles have an average particle size of 10-30 microns, and the GHDR-15-4 particles have a vapor-deposited coating of carbon on the outer surface of the PSG particles.

The uncured resin matrix may contain small amounts (less than 5% by weight, preferably less than 1% by weight) of additional epoxy or non-epoxy thermosetting polymer resins. In the case of DEN/TRIF/TETF matrix resins, the epoxy resin component contains at least 95% by weight of DEN, TRIF and TETF, more preferably at least 99% by weight of three epoxy resins. In the case of DEN/TRIF matrix resins, the epoxy resin component contains at least 95% by weight of DEN and TRIF, more preferably at least 99% by weight of two epoxy resins. Suitable additional epoxy resins include difunctional epoxy resins, such as bisphenol A and bisphenol F type epoxy resins. Non-epoxy thermosetting resin materials suitable for the present invention include, but are not limited to, phenol formaldehyde, urea-formaldehyde, 1,3,5 triazine-2,4,6 triamine (melamine), bismaleimide, vinyl ester resin, benzoxazine resin, phenolic resin, polyester, cyanate ester resin, or any combination thereof. Additional thermosetting resins, when present, are preferably selected from epoxy resins, cyanate ester resins, benzoxazine and phenolic resins.

The uncured resin is made according to standard prepreg matrix resin processing. Generally, the hydrocarbon novolac epoxy resin and other epoxy resins are mixed together at room temperature to form a resin mix to which the thermoplastic toughening agents are added. This mixture is then heated to about 120°C for about 1-2 hours to dissolve the thermoplastic toughening agents. The mixture is then cooled to about 80°C and the remaining ingredients (thermoplastic particulate components, if present, hardeners and other additives) are mixed into the resin to form the final uncured resin matrix that is impregnated into the fiber reinforcement.

The uncured resin is applied to the fiber reinforcement to form an uncured resin matrix according to any of the known prepreg manufacturing techniques. The fiber reinforcement may be fully or partially impregnated with the uncured resin. In an alternative embodiment, the uncured resin may be applied to the fiber reinforcement as a separate layer that is in close proximity to and in contact with the fiber reinforcement but does not substantially impregnate the fiber reinforcement. Prepregs, also called semipregs, are usually coated on both sides with a protective film to avoid premature curing, and are usually rolled up for storage and transportation at temperatures well below room temperature. The actual resin matrix is not formed until further processing of the semipreg. Any of the other prepreg manufacturing processes and storage/shipping systems may be used if desired.

The fiber reinforcement of the prepreg may be selected from any fiberglass, carbon or aramid (aromatic polyamide) fiber. Preferably, the fiber reinforcement is carbon fiber. Preferred carbon fiber is in the form of a tow containing 3,000 to 50,000 carbon filaments (3K to 50K). Commercially available carbon fiber tows containing 6,000 or 24,000 carbon filaments (6K or 24K) are preferred.

The uncured matrix resin of the present invention is particularly effective in providing laminates with high strength properties and damage tolerance when the carbon tow contains 6,000-24,000 filaments, has a tensile strength of 750-860 Ksi, a tensile modulus of 35-45 Msi, a strain to break of 1.5-2.5%, a density of 1.6-2.0 g/ ^cm3 , and a weight per length of 0.2-0.6 g/m3. 6K and 12K IM7 carbon tows (available from Hexcel Corporation) are preferred. IM7 12K fibers have a tensile strength of 820 Ksi, a tensile modulus of 40 Msi, a strain to break of 1.9%, a density of 1.78 g/ ^cm3 , and a weight per length of 0.45 g/m3. IM7 6K fiber has a tensile strength of 800 Ksi, a tensile modulus of 40 Msi, a strain to failure of 1.9%, a density of 1.78 g/ ^cm3 , and a weight per length of 0.22 g/m. IM7 fiber and carbon fibers with similar properties are generally considered to be intermediate modulus carbon fibers. IM8 carbon fiber, available from Hexcel Corporation (Dublin, Calif.), is also a preferred type of intermediate modulus carbon fiber.

The fiber reinforcement may include cracked (i.e., stretch-broken) or selectively discontinuous fibers, or continuous fibers. The use of cracked or selectively discontinuous fibers may facilitate layup of the composite before it is fully cured and improve its shaping ability. The fiber reinforcement may be in the form of a woven, non-crimped, non-woven, unidirectional, or multiaxial woven structure, such as, for example, quasi-isotropic chopped prepregs used to form sheet molding compounds. The woven forms may be selected from plain, satin, or twill styles. The non-crimped and multiaxial forms may have several layers and fiber orientations. Such styles and forms are well known in the composite reinforcement art and are commercially available from several companies, including Hexcel Reinforcements (Les Avenieres, France).

Prepregs may be in the form of continuous tapes, towpregs, webs, or chopped lengths (chopping and slitting operations may be performed at any time after impregnation). Prepregs may be adhesive or surfacing films and may have embedded carriers of various forms, both woven, knitted, and nonwoven. Prepregs may be fully or only partially impregnated, for example to facilitate air removal during curing.

The following exemplary DEN/TRIF/TETF resin formulations may be impregnated into a fibrous support to form a resin matrix in accordance with the present invention (all weight percentages are based on total resin weight):
12% to 16% by weight of dicyclopentadiene novolac epoxy resin (TACTIX® 556 or XD-1000-2L); 17% to 21% by weight of triglycidyl-p-aminophenol (MY0510); 16% to 20% by weight of tetrafunctional epoxy (MY721); 10% to 14% by weight of polyethersulfone (5003P); 2% to 4% by weight of polyimide particles (P84HCM); 7% to 11% by weight of hybrid polyamide particles; and 24% to 28% by weight of 3,3'-DDS as a curing agent.

Regarding the DEN/TRIF matrix resin embodiment of the present invention, an exemplary DEN/TRIF matrix resin includes 34% to 38% by weight triglycidyl-m-aminophenol (MY0600); 16% to 20% by weight hydrocarbon novolac epoxy resin (TACTIX 556 or XD-1000-2L); 7% to 11% by weight polyethersulfone (5003P) as a toughening agent; 2% to 7% by weight crosslinked polyamide 12 particles (ORGASOL 2009); 9% to 13% by weight hybrid polyamide particles, the hybrid polyamide particles having a weight ratio of hybrid polyamide particles to crosslinked polyamide 12 particles of 2.5:1.0 to 3.0:1, preferably 2.7:1 to 2.8:1; and 20% to 26% by weight 4,4'-DDS as a curing agent.

Another exemplary DEN/TRIF matrix resin includes 34% to 38% by weight triglycidyl-m-aminophenol (MY0600); 16% to 20% by weight hydrocarbon novolac epoxy resin (TACTIX 556 or XD-1000-2L); 7% to 11% by weight polyethersulfone (5003P) as a toughening agent; 9% to 13% by weight polyamide 11 particles (Rislan PA11); 2% to 4% by weight hybrid polyamide particles; and 20% to 26% by weight 4,4'-DDS as a curing agent.

A preferred DEN/TRIF matrix resin comprises 34% to 38% by weight triglycidyl-m-aminophenol (MY0600); 16% to 20% by weight hydrocarbon novolac epoxy resin (TACTIX 556 or XD-1000-2L); 7% to 11% by weight polyethersulfone (5003P) as a toughening agent; 13% to 17% by weight hybrid polyamide particles; and 20 % to 26% by weight 4,4'-DDS as a curing agent.

The prepregs can be molded using any of the standard techniques used to form composite parts. Typically, one or more layers of the prepregs are placed in a suitable mold and cured to form the final composite part. The prepregs of the present invention can be fully or partially cured using any suitable temperature, pressure, and time conditions known in the art; typically, the prepregs will be cured in an autoclave at temperatures between 160°C and 190°C. The composites can be cured using a method selected from microwave radiation, electron beam, gamma radiation, or other suitable thermal or non-thermal radiation.

Composite parts made from the improved prepregs of the present invention find use in the manufacture of articles such as primary and secondary aerospace structures (such as wings, fuselages and bulkheads), but are also useful in many other high performance composite applications, including automotive, rail and marine applications where high compressive strength, interlaminar fracture toughness and impact damage resistance are required.

Examples 1 and 2, which are examples of embodiments of the DEN/TRIF/TETF matrix resin of the present invention, are as follows:

Example 1
A preferred exemplary resin formulation according to the present invention is shown in Table 1. The matrix resin was prepared by mixing the epoxy component with the polyethersulfone at room temperature to form a resin blend, which was heated to 120° C. for 60 minutes to completely dissolve the polyethersulfone. The mixture was cooled to 80° C. and the remaining components were added and thoroughly mixed.

The hybrid polyamide particles used in the following examples are described according to the weight percent of amorphous (TROGAMID CX9704) and semi-crystalline (TROGAMID CX9705) polyamide present in each particle. As noted above, the hybrid polyamide particles containing a mixture of 70% by weight CX9704 polyamide and 30% by weight CX9705 polyamide are identified as hybrid particles "(70A/30SC)" and the hybrid polyamide particles containing a mixture of 30% by weight CX9704 polyamide and 70% by weight CX9705 polyamide are identified as hybrid polyamide particles "(30A/70SC)." The hybrid polyamide particles used in the examples, as well as the amorphous and semi-crystalline particles used in the comparative examples, ranged in size from 3 microns to 10 microns with an average particle size of 6 microns.

Exemplary prepregs were prepared by impregnating one or more layers of unidirectional carbon fiber with the resin formulations in Table 1. Unidirectional carbon fiber (12K IM7 available from Hexcel Corporation) was used to make prepregs with matrix resin at 35 weight percent of the total uncured prepreg weight and fiber areal weight of 192 grams per square meter (gsm). Standard prepreg manufacturing procedures were used to prepare 26-ply laminates. The laminates were cured in an autoclave at 177°C for approximately 2 hours. The cured laminates were tested to determine interlaminar fracture toughness.

G2c is a standard test that gives a measure of the interlaminar fracture toughness of a cured laminate. G2c was determined as follows: A 26-ply unidirectional laminate was cured with a 3-inch fluoroethylene polymer (FEP) film inserted along one edge at the mid-face of the layup, perpendicular to the fiber direction, to act as a crack starter. The laminate was cured in an autoclave at 177°C for 2 hours to give a nominal thickness of 3.8 mm. G2c specimens were machined from the cured laminates where consolidation was confirmed by C-scan. G2c was tested at room temperature according to BSS7320. The G2c values reported below are the average of the first and second cracks observed during testing according to BSS7320.

The cured test laminates were subjected to standard tests to determine damage tolerance (CAI) and interlaminar fracture toughness (G1c and G2c). Compression after impact (CAI) was determined using a 270 in-lb impact on a 32-ply quasi-isotropic laminate. Specimens were machined, impacted, and tested according to Boeing test method BSS 7260 per BMS 8-276. Values are normalized to a nominal cured laminate thickness of 0.18 inches.

When the terms "CAI" and "G2c" are used herein to define properties exhibited by a cured laminate, the terms refer to the properties as measured by the test procedures set forth above.

The G2c of the cured 26-ply laminate was 12.6. The CAI was 46.0. Open hole compression (OHT) and open hole compression (OHC) were also measured at room temperature per standard procedures and were found to be beyond the acceptable limits for the structural components.

Example 2
An exemplary prepreg having a DEN/TRIF/TETR resin matrix having the formula shown in Table 2 was prepared similarly to Example 1.

A 26-ply laminate was prepared as in Example 1, cured at room temperature, and tested for G2c. G2c was 11.8 and CAI was 43.6. Both OHT and OHC were also above the acceptable limits for structural parts. The G2c and CAI values for Example 2 (hybrid particles 30A/70SC) are unexpectedly lower than those for Example 1 (hybrid particles 70A/30SC), where the amount of amorphous polyamide in the particles is substantially greater than the amount of semi-crystalline polyamide. Thus, as previously mentioned, the hybrid polyamide particles preferably contain 60% to 80% by weight of amorphous polyamide and 20% to 40% by weight of semi-crystalline polyamide.

The first comparative example was run replacing the hybrid polyamide particles used in Examples 1 and 2 with semi-crystalline polyamide particles made from Trogamid (registered trademark in some countries) CX9705 polyamide. As in Example 1, a 26-ply laminate was prepared, cured at room temperature, and tested for G2c. G2c was 9.0. CAI was 43.0. It was unexpected that the G2c and CAI would be lower when hybrid particles containing a mixture of semi-crystalline and amorphous forms of the same polyamide were replaced with particles containing only the semi-crystalline form of the polyamide.

A second comparative example was performed by replacing the hybrid polyamide particles used in Examples 1 and 2 with amorphous polyamide particles made from Trogamid CX9704 polyamide. As in Example 1, a 26-ply laminate was prepared, cured at room temperature, and tested for G2c. The G2c was 10.0 and the CAI was 44.9. As described in Example 1, it was unexpected that the G2c and CAI would be lower when hybrid particles containing a 70A/30SC mixture of amorphous and semi-crystalline forms of the same polyamide were replaced with particles containing only the amorphous form. As described in Example 2, it was also unexpected that the G2c of the second comparative example was lower and the CAI of the second comparative example was higher than Example 2 when hybrid particles containing a 30A/70SC mixture of amorphous and semi-crystalline forms of the same polyamide were replaced with particles containing only the amorphous form.

All of the above examples and comparative examples use polyamide particles made from polyamides having the same monomer units (Formula II). It is unexpected that hybrid polyamide particles containing a mixture of amorphous and semi-crystalline forms of the same polymer, respectively, can provide higher G2c and CAI test results than can be achieved using only the amorphous or semi-crystalline forms of the polyamide.

Examples 3 to 5, which are implementation examples of the DEN/TRIF matrix resin embodiment of the present invention, are as follows.

Example 3
Exemplary DEN/TRIF resin formulations according to the invention are shown in Table 3. The uncured matrix resin was prepared by mixing the epoxy components with polyethersulfone at room temperature to form a resin blend, which was then heated to 120° C. for 60 minutes to completely dissolve the polyethersulfone. As in Examples 1-2, the mixture was cooled to 80° C. and the remaining components were added and mixed thoroughly.

An exemplary prepreg was prepared by impregnating a layer of unidirectional carbon fiber with the resin formulation in Table 3 to form a prepreg composed of reinforcing fibers and an uncured resin matrix. The unidirectional carbon fiber was 12K IM7. The uncured resin matrix made up 35% by weight of the total uncured prepreg weight, and the fiber areal weight of the uncured prepreg was 145 grams per square meter (gsm).

The prepregs were used to form laminates as in Examples 1-2. The laminates were cured in an autoclave at 177°C for approximately 2 hours to form cured test laminates. The cured test samples were tested in accordance with ASTM D5528 to determine G2c and CAI in the same manner as in Examples 1-2. G2c was determined to be 18.1 and CAI was 55.9.

A comparative example was run where the hybrid polyamide particles used in Example 3 were replaced with semi-crystalline polyamide particles made from Trogamid CX9705 polyamide. As in Example 1, a 26-ply laminate was prepared, cured at room temperature, and tested for CAI and G2c. The CAI was 50.0 and the G2c was 12.4. It was unexpected that the G2c would be lower when hybrid particles containing a mixture of semi-crystalline and amorphous forms of the same polyamide were replaced with particles containing only the semi-crystalline form of the polyamide.

A second comparative example was run replacing the hybrid polyamide particles used in Example 3 with amorphous polyamide particles made from Trogamid CX9704 polyamide. As in Example 1, a 26-ply laminate was prepared, cured at room temperature, and tested for CAI and G2c. The CAI was 63.2 and the G2c was 17.8. As described in Example 1, it was unexpected that the G2c would be lower when hybrid particles containing a mixture of amorphous and semi-crystalline forms of the same polyamide were replaced with particles containing only the amorphous form. The results are particularly unexpected in view of the substantially lower G2c observed in the first comparative example.

All of the above examples and comparative examples use polyamide particles made from polyamides having the same monomer units (Formula II). It is unexpected that hybrid polyamide particles containing a mixture of amorphous and semi-crystalline forms of the same polymer, respectively, can provide higher G2c test results than can be achieved using only the amorphous or semi-crystalline forms of the polyamide.

Example 4
Exemplary prepregs having a DEN/TRIF resin matrix with the formula shown in Table 4 were prepared similarly to Example 3.

A 26-ply laminate was prepared as in Example 1, cured at room temperature, and tested for CAI and G2c. The CAI was 61.6 and the G2c was 16.4. Both the OHT and OHC were also above the acceptable limits for the structural part.

Example 5
An exemplary prepreg having a DEN/TRIF resin matrix having the formula shown in Table 5 was prepared similarly to Example 3.

A 26-ply laminate was prepared as in Example 1, cured at room temperature, and tested for CAI and G2c. The CAI was 61.2 and the G2c was 16.5. Both the OHT and OHC were also above the acceptable limits for the structural part.

Having thus described exemplary embodiments of the present invention, those skilled in the art should note that the scope of the disclosure is merely exemplary, and that various other changes, modifications, and alterations may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but only by the appended claims.
Note that the following [1] to [20] are each one embodiment or one aspect of the present invention.
[1]
1. A pre-impregnated composite material comprising:
A) reinforcing fibers;
B) an uncured resin matrix,
a) epoxy resin component;
b) a thermoplastic particle component comprising hybrid polyamide particles, each of said hybrid polyamide particles comprising a mixture of semi-crystalline polyamide and amorphous polyamide, said amorphous polyamide being present in an amount of 20-80% by weight based on the total weight of said hybrid polyamide particles, said semi-crystalline polyamide being present in an amount of 20-80% by weight based on the total weight of said hybrid polyamide particles, said semi-crystalline polyamide and said amorphous polyamide being reacted with 1,10-decanedicarboxylic acid and a compound of the formula

a thermoplastic particle component, which is a different stereoisomeric form of said polyamide, composed of a polymer condensation product with an amine component having
c) a thermoplastic toughening agent comprising polyethersulfone; and
d) Hardener
An uncured resin matrix comprising
A pre-impregnated composite material comprising:
[2]
2. The pre-impregnated composite material according to claim 1, wherein the amorphous polyamide is present in an amount of 65 to 75 wt. %, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 25 to 35 wt. %, based on the total weight of the hybrid polyamide particles.
[3]
3. The pre-impregnated composite material according to claim 2, wherein the amorphous polyamide is present in an amount of 70±1 wt.%, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 30±1 wt.%, based on the total weight of the hybrid polyamide particles.
[4]
2. The pre-impregnated composite material according to claim 1, wherein the thermoplastic particulate component further comprises polyamide 11 particles.
[5]
2. The pre-impregnated composite material of claim 1, wherein the thermoplastic particulate component further comprises crosslinked polyamide 12 particles.
[6]
2. The pre-impregnated composite material according to claim 1, wherein the thermoplastic particulate component further comprises polyimide particles.
[7]
2. The pre-impregnated composite material of claim 1, wherein the reinforcing fibers comprise a plurality of carbon fiber tows each having 10,000 to 14,000 carbon filaments, each of the carbon tows having a weight per length of 0.2 to 0.6 grams per meter, each of the carbon tows having a tensile strength of 750 to 860 kilopounds per square inch, and each of the carbon tows having a tensile modulus of 35 to 45 megapounds per square inch.
[8]
The pre-impregnated composite material of [1], wherein the curing agent is an aromatic amine selected from the group consisting of 3,3'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone.
[9]
1. A composite part or structure formed by curing the pre-impregnated composite material according to claim 1.
[10]
10. The composite part or structure of claim 9, wherein the composite part or structure forms at least a part of a primary structure of an aircraft.
[11]
1. A method of making a pre-impregnated composite material capable of curing to form a composite part, comprising:
A) providing reinforcing fibers comprising carbon fibers; and
B) impregnating the reinforcing fibers with an uncured resin matrix, the uncured resin matrix being:
a) epoxy resin component;
b) a thermoplastic particle component comprising hybrid polyamide particles, each of said hybrid polyamide particles comprising a mixture of semi-crystalline polyamide and amorphous polyamide, said amorphous polyamide being present in an amount of 20-80% by weight based on the total weight of said hybrid polyamide particles, said semi-crystalline polyamide being present in an amount of 20-80% by weight based on the total weight of said hybrid polyamide particles, said semi-crystalline polyamide and said amorphous polyamide being reacted with 1,10-decanedicarboxylic acid and a compound of the formula

a thermoplastic particle component, which is a different stereoisomeric form of said polyamide, composed of a polymer condensation product with an amine component having
c) a thermoplastic toughening agent comprising polyethersulfone; and
d) Hardener
Including steps
A method of making a pre-impregnated composite material comprising:
[12]
12. The method of making a pre-impregnated composite material according to claim 11, wherein the amorphous polyamide is present in an amount of 65 to 75 wt. %, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 25 to 35 wt. %, based on the total weight of the hybrid polyamide particles.
[13]
12. The method of making a pre-impregnated composite material capable of forming a composite part by curing according to claim 11, wherein the amorphous polyamide is present in an amount of 70±1 wt.%, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 30±1 wt.%, based on the total weight of the hybrid polyamide particles.
[14]
12. The method of making a pre-impregnated composite material capable of forming a composite part upon curing according to claim 11, wherein the thermoplastic particulate component further comprises polyamide 11 particles.
[15]
12. The method of making a pre-impregnated composite material capable of forming a composite part upon curing according to claim 11, wherein the thermoplastic particulate component further comprises crosslinked polyamide 12 particles.
[16]
12. The method of making a pre-impregnated composite material capable of forming a composite part upon curing according to claim 11, wherein the thermoplastic particulate component further comprises polyimide particles.
[17]
12. The method of making a pre-impregnated composite material capable of curing to form a composite part according to claim 11, wherein the reinforcing fibers comprise a plurality of carbon fiber tows each having 10,000 to 14,000 carbon filaments, each of the carbon tows having a weight per length of 0.2 to 0.6 grams per meter, each of the carbon tows having a tensile strength of 750 to 860 kilopounds per square inch, and each of the carbon tows having a tensile modulus of 35 to 45 megapounds per square inch.
[18]
12. The method of making a pre-impregnated composite material capable of forming a composite part by curing according to claim 11, wherein the curing agent is an aromatic amine selected from the group consisting of 3,3′-diaminodiphenylsulfone and 4,4′-diaminodiphenylsulfone.
[19]
12. A method of making a composite part or structure comprising providing a pre-impregnated composite material according to claim 11 and curing the pre-impregnated composite material to form a composite part or structure.
[20]
20. The method of making a composite part or structure according to [19], wherein the composite part or structure forms at least part of a primary structure of an aircraft.

Claims (14)

1. A pre-impregnated composite material comprising:
A) reinforcing fibers;
B) an uncured resin matrix,
a) epoxy resin component;
b) a thermoplastic particle component comprising a mixture of polyimide particles and hybrid polyamide particles, each of the hybrid polyamide particles comprising a mixture of semi-crystalline polyamide and amorphous polyamide, the amorphous polyamide being present in an amount of 60-80 wt. % based on the total weight of the hybrid polyamide particles, the semi-crystalline polyamide being present in an amount of 20-40 wt. % based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide and amorphous polyamide being reacted with 1,10-decanedicarboxylic acid and a compound of the formula

a thermoplastic particle component, which is a different stereoisomeric form of said polyamide, composed of a polymer condensation product with an amine component having
A pre-impregnated composite material comprising: an uncured resin matrix comprising: c) a thermoplastic toughening agent comprising polyethersulfone; and d) a curing agent. The pre-impregnated composite material of claim 1, wherein the amorphous polyamide is present in an amount of 65 to 75 wt % based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 25 to 35 wt % based on the total weight of the hybrid polyamide particles. The pre-impregnated composite material of claim 2, wherein the amorphous polyamide is present in an amount of 70±1 wt.% based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 30±1 wt.% based on the total weight of the hybrid polyamide particles. The pre-impregnated composite material of claim 1, wherein the reinforcing fibers include a plurality of carbon fiber tows each containing 10,000-14,000 carbon filaments, each of the carbon tows having a weight per length of 0.2-0.6 grams/meter, each of the carbon tows having a tensile strength of 750-860 kilopounds/square inch, and each of the carbon tows having a tensile modulus of 35-45 megapounds/square inch. The pre-impregnated composite material of claim 1, wherein the curing agent is an aromatic amine selected from the group consisting of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone. A composite part or structure formed by curing the pre-impregnated composite material of claim 1. The composite part or structure of claim 6 , wherein the composite part or structure forms at least a portion of a primary structure of an aircraft. 1. A method of making a pre-impregnated composite material capable of curing to form a composite part, comprising:
A) providing reinforcing fibers comprising carbon fibers; and B) impregnating the reinforcing fibers with an uncured resin matrix, the uncured resin matrix comprising:
a) epoxy resin component;
b) a thermoplastic particle component comprising a mixture of polyimide particles and hybrid polyamide particles, each of the hybrid polyamide particles comprising a mixture of semi-crystalline polyamide and amorphous polyamide, the amorphous polyamide being present in an amount of 60-80 wt. % based on the total weight of the hybrid polyamide particles, the semi-crystalline polyamide being present in an amount of 20-40 wt. % based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide and amorphous polyamide being reacted with 1,10-decanedicarboxylic acid and a compound of the formula

a thermoplastic particle component, which is a different stereoisomeric form of said polyamide, composed of a polymer condensation product with an amine component having
c) a thermoplastic toughening agent comprising polyethersulfone; and d) a curing agent. 9. The method of making a pre-impregnated composite material according to claim 8, wherein the amorphous polyamide is present in an amount of 65 to 75 wt %, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 25 to 35 wt %, based on the total weight of the hybrid polyamide particles. 9. The method of making a pre-impregnated composite material capable of curing to form a composite part according to claim 8, wherein the amorphous polyamide is present in an amount of 70±1 wt%, based on the total weight of the hybrid polyamide particles, and the semi-crystalline polyamide is present in an amount of 30± 1 wt%, based on the total weight of the hybrid polyamide particles. 9. The method of making a pre-impregnated composite material capable of curing to form a composite part as recited in claim 8, wherein the reinforcing fibers comprise a plurality of carbon fiber tows each having 10,000 to 14,000 carbon filaments, each of the carbon tows having a weight per length of 0.2 to 0.6 grams per meter, each of the carbon tows having a tensile strength of 750 to 860 kilopounds per square inch, and each of the carbon tows having a tensile modulus of 35 to 45 megapounds per square inch . 9. The method of making a pre-impregnated composite material capable of being cured to form a composite part as recited in claim 8 , wherein the curing agent is an aromatic amine selected from the group consisting of 3,3'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone. 10. A method of making a composite part or structure comprising providing a pre-impregnated composite material according to claim 8 and curing the pre-impregnated composite material to form a composite part or structure. The method of making a composite part or structure according to claim 13 , wherein the composite part or structure forms at least a portion of a primary structure of an aircraft.

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